CN114787205B - Preparation of aqueous dispersions of blocked polymer particles - Google Patents
Preparation of aqueous dispersions of blocked polymer particles Download PDFInfo
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- CN114787205B CN114787205B CN202080086208.3A CN202080086208A CN114787205B CN 114787205 B CN114787205 B CN 114787205B CN 202080086208 A CN202080086208 A CN 202080086208A CN 114787205 B CN114787205 B CN 114787205B
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The present invention relates to a process for preparing an aqueous dispersion of heterophasic closed polymer particles, the process comprising the steps of: a) Contacting the first monomer and the chain transfer agent under emulsion polymerization conditions to form a polymer having a T in the range of from-30 ℃ to 30 DEG C g An aqueous dispersion of first polymer particles of (a); then b) contacting the aqueous dispersion of first polymer particles with a second monomer under emulsion polymerization conditions to form an aqueous dispersion of second polymer particles enclosed within the first polymer particles, wherein the first monomer is a phosphoric acid monomer or salt thereof; and the second monomer comprises at least 90 wt% methyl methacrylate. The aqueous dispersion of the blocked polymer particles produced by the method of the invention can be used in a formulation that can be used to prepare a water resistant bubble cap LASD coating.
Description
Background
Damping materials are used to dampen vibrations in rigid structures to reduce noise. In motor vehicles, two main vibration damping techniques dominate: asphalt mats and liquid-applied acoustic damping (LASD) coatings derived from aqueous latex. Asphalt mats are a low cost alternative widely used in the 20 th century, exhibit relatively poor damping properties, and require laborious manual application. On the other hand, LASD coatings have gained significant market share because they can be applied rapidly by robotic spray techniques. In addition, LASD coatings exhibit better damping characteristics, environmental, health and safety (EH & S) curves, and lower densities. In summary, these benefits have led to the automotive OEMs increasingly employing laser for Noise Vibration and Hazard (NVH) management over existing asphalt mats. WO 2018/062546 A1 describes aqueous dispersions of polymer particles suitable for vibration damping applications. Although the improvement in foaming inhibition was reported, the water resistance was not described. There remains a need in the art to develop a LASD coating having superior water resistance compared to asphalt mats. The water resistant LASD coating may assist customers in utilizing the present technology. In addition, the improved water resistance may allow the LASD coating to be used in new application areas, such as in the wheel well of a vehicle. Accordingly, it would be an advancement in the art to develop aqueous dispersions of polymer particles that can be formulated into LASD coatings that are water resistant, exhibit excellent appearance and maintain high vibration damping properties.
Disclosure of Invention
The present invention is a process for preparing an aqueous dispersion of heterophasic closed polymer particles, comprising the steps of: a) Contacting the first monomer and the chain transfer agent under emulsion polymerization conditions to form a polymer having a T in the range of from-30 ℃ to 30 DEG C g Wherein the concentration of chain transfer agent is from 0.5 mole% to 1 based on the moles of first monomer and chain transfer agent.5 mol%; then b) contacting the aqueous dispersion of first polymer particles with a second monomer under emulsion polymerization conditions to form an aqueous dispersion of second polymer particles enclosed within the first polymer particles, wherein the first monomer comprises from 0.2 to 5 weight percent of a phosphoric acid monomer or salt thereof, based on the weight of the first monomer; the second monomer comprises at least 90% by weight methyl methacrylate; and wherein the weight to weight ratio of the first monomer to the second monomer is in the range from greater than 80:20 and less than 95:5.
The present invention addresses the need in the art by providing an aqueous composition that forms a blister-free coating useful for sound damping applications.
Detailed Description
The present invention is a process for preparing an aqueous dispersion of heterophasic closed polymer particles, comprising the steps of: a) Contacting the first monomer and the chain transfer agent under emulsion polymerization conditions to form a polymer having a T in the range of from-30 ℃ to 30 DEG C g Wherein the concentration of chain transfer agent is from 0.5 mole% to 1.5 mole% based on the moles of first monomer and chain transfer agent; then b) contacting the aqueous dispersion of first polymer particles with a second monomer under emulsion polymerization conditions to form an aqueous dispersion of second polymer particles enclosed within the first polymer particles, wherein the first monomer comprises from 0.2 to 5 weight percent of a phosphoric acid monomer or salt thereof, based on the weight of the first monomer; the second monomer comprises at least 90% by weight methyl methacrylate; and wherein the weight to weight ratio of the first monomer to the second monomer is in the range from greater than 80:20 and less than 95:5.
The first polymer particles are advantageously prepared by contacting the first monomer and the chain transfer agent under emulsion polymerization conditions to form a polymer having a T in the range of-30 ℃, preferably from-20 ℃ to 30 ℃, preferably to 20 ℃, more preferably to 10 ℃ as calculated from the Fox equation g Wherein the concentration of chain transfer agent is from 0.5 mole%, preferably from 0.7 mole%, based on the moles of first monomer and chain transfer agentMore preferably from 1 to 1.5 mole%, preferably to 1.3 mole%, more preferably to 1.2 mole%.
Chain transfer agents are any compound capable of adjusting the molecular weight of the polymer during the polymerization process. Particularly suitable chain transfer agents include alkyl mercaptans such as n-dodecyl mercaptan (n-DDM) and t-dodecyl mercaptan (t-DDM).
As used herein, "first monomer" refers to a monomer selected to form a polymer having a T in the range of from-30 ℃ to 30 ° g Is a monomer of the first polymer particles of (a). Preferred first monomers comprise a) Methyl Methacrylate (MMA) or styrene; and b) one or more monomers selected from the group consisting of: butyl Acrylate (BA), ethyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate, preferably a combination of MMA and BA. The first monomer further comprises from 0.2 wt%, more preferably from 0.5 wt%, more preferably from 0.8 wt%, and most preferably from 1.0 wt% to 5 wt%, more preferably to 3 wt%, and most preferably to 2 wt% of structural units of a phosphoric acid monomer or salt thereof, based on the weight of the first polymer particles. Examples of suitable phosphoric acid monomers include phosphonates and dihydrogen phosphates of alcohols containing or substituted by a polymerisable vinyl or alkenyl group. Preferred dihydrogen phosphates are hydroxyalkyl (meth) acrylates, including phosphoethyl methacrylate and phosphopropyl methacrylate, with phosphoethyl methacrylate being particularly preferred. "phosphoethylmethacrylate" (PEM) is used herein to refer to the structure:
wherein R is H or
Wherein the dotted line represents the point of attachment to the oxygen atom.
Advantageously preparing second polymer particles in a second step after substantial or complete polymerization of the first monomer by contacting the aqueous dispersion of first polymer particles with the second monomer under emulsion polymerization conditions; the second monomer preferably comprises at least 92 wt%, more preferably at least 95 wt%, more preferably at least 98 wt%, and more preferably at least 99 wt% methyl methacrylate. The second monomer may comprise up to 8 wt% of another monomer, such as methacrylic acid (MAA).
The first monomer and the second monomer form a structural unit upon polymerization. As used herein, the term "structural unit" of a given monomer refers to the residue of the monomer after polymerization. For example, the structural units of MMA are as follows:
wherein the dashed lines represent attachment points of the building blocks to the polymer backbone.
With formation of stacks of low T as disclosed in WO 2018/062546 A1 g The different outer layers of the polymer particles are reversed, followed by a high T g Second Polymer particles at low T g Discrete high T formation within first polymer particles of (soft) domains g (hard) domain. The discrete domains are referred to as blocking (binding to) the first polymer particles. Occlusion was confirmed by atomic force microscopy. A discussion and description of the morphology of the closed multiphase latex particles can be found in J.coat.technology.
Res, 5 (2) 169-180, 2008. Preferably, the weight to weight ratio of the occluded second polymer particles to the first polymer particles is preferably in the range from 6:94, more preferably from 8:92 to 19:81, more preferably to 17:83.
The capped polymer particles preferably have a z-average particle size in the range from 80nm, and more preferably 100nm to 400nm, more preferably to 300nm, and most preferably to 200nm by dynamic light scattering. The polymer particles preferably have an M in the range of from 10,000, more preferably from 11,000g/mol to preferably 22,000, more preferably to 18,000, more preferably to 15,000, most preferably to 13,000g/mol n (measured by gel permeation chromatography as described below).
The solids content of the aqueous dispersion of closed heterophasic polymer particles is preferably in the range of 20 to 60 wt%. Preferably, the heterophasic polymer particles are 2-phase polymer particles.
The aqueous dispersion of the blocking polymer particles is advantageously used as part of a formulation suitable for LASD applications. The formulation comprises at least one additive selected from the group consisting of: extenders, baking additives (such as starches) and rheology modifiers. Preferably, the formulation comprises all these additives.
The formulation also preferably comprises a nonionic compound of structure I:
wherein R is 1 Is H or C 6 -C 18 An alkyl group; r is R 2 Is H or CH 3 The method comprises the steps of carrying out a first treatment on the surface of the And x is from 30, preferably from 45, and more preferably from 80; to 300, preferably to 250, and more preferably to 200.
A preferred nonionic compound is polyethylene glycol (wherein R 1 Is H) or polyethylene oxide secondary alcohol ethoxylate (wherein R 1 Is branched alkyl). Suitable commercially available nonionic compounds include CARBOWAX TM PEG 4000 and 8000 polyethylene glycols (PEG 4000 and PEG 8000, respectively) and TERGITOL TM 15-S-20 and 15-S-40 secondary alcohol ethoxylates (trademark of Dow chemical Co., or its affiliated).
The concentration of the nonionic compound of structure I in the formulation is preferably in the range from 0.2 wt%, more preferably from 0.5 wt% to 5 wt%, more preferably to 3 wt%, and most preferably to 2 wt%, based on the weight of the formulation.
It has been found that, at a defined narrow M n Phosphoric acid functionalization (preferably PEM functionalization) of soft domains of range-blocked polymer particles versus texture, sudsing and water absorption curves of formulations comprising these blocked polymer particlesHas particularly beneficial effects; furthermore, it has been found that the inclusion of nonionic compounds of structure I in the formulation, as well as phosphoric acid functionalized blocked polymer particles, can improve these key properties.
It has surprisingly been found that coatings suitable for vibration damping applications can be prepared with desirable textures, very low water absorption, and little or no evidence of foaming.
n Gel permeation chromatography method for measuring M of closed particles
GPC samples were prepared in THF at a concentration of 5mg/mL based on blocked polymer solids content. The sample solution was kept overnight on a plate shaker at room temperature and then filtered through a 0.45 μm PTFE filter (Whatman) prior to GPC analysis. The GPC instrument setup consisted of an Agilent 1200 series HPLC system (degasser, pump, autosampler) and a Wyatt T-rEX refractive index detector. Polymer separation was performed on a column set consisting of a TOSOH TSKgel GMH xl L and a TOSOH TSKgel G5000H xl Columns (each packed with 9 μm styrene divinylbenzene gel; 7.5mm ID. Times.30 cm each) were made up, the separation using THF as the mobile phase at a flow rate of 1mL/min; the sample loading was 40. Mu.L.
Data acquisition and processing was performed using Astra 7 software (Huai Ya tricks Technology). M was calculated using a conventional calibration method based on polystyrene standards (Agilent technologies Co.) n And M w As shown in table 1 below:
TABLE 1 polystyrene standards
The number average molecular weight and weight average molecular weight were obtained based on the polystyrene calibration curve and the sample elution curve by the following equations:
wherein h is based on a polystyrene calibration curve i Height of GPC curve at ith volume increment and M i Molecular weight of the material eluting at the ith retention volume.
Examples
Example 1 preparation of an aqueous Dispersion of 2-stage blocked Polymer particles with 10% hard stage
A first monomer emulsion was prepared by mixing deionized water (492 g), sodium lauryl ether sulfate (43 g,31% active material in water), BA (1066 g,8.32 moles), MMA (797 g,7.96 moles), PEM (43 g,60% active material, 0.12 moles) and n-DDM (37 g,0.18 moles). A second monomer emulsion was prepared by mixing deionized water (134 g), sodium lauryl ether sulfate (5 g, 30% active material in water), and MMA (214 g,2.14 moles).
Deionized water (881 g) and sodium lauryl ether sulfate (2.4 g,31% active material) were added to a 5-L four-necked round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser. The contents of the flask were heated to 84 ℃ under nitrogen and stirring was started. A portion of the first monomer emulsion (132 g) was then added quickly followed by a solution of ammonium persulfate (5 g) in deionized water (55 g). After stirring for 10 minutes, the remainder of the first monomer emulsion and an initiator solution of ammonium persulfate (2.1 g) in deionized water (90 g) were added over 80 minutes, respectively. The contents of the flask were maintained at 84 ℃ for 10 minutes, after which a second monomer emulsion and an initiator solution containing sodium persulfate (0.2 g) in deionized water (10 g) were added to the flask, respectively, over a period of 10 minutes.
The batch is then cooled and the residue reduced with a redox coupleThe monomer was left and then neutralized to pH9. The z-average particle size was measured by a Brookhaven BI-90Plus particle size analyzer to be 165nm and found to be 51% solids. M found calculated by gel permeation chromatography n Is 12,000g/mol.
EXAMPLE 2 preparation of an aqueous Dispersion of 2-stage blocked Polymer particles with 15% hard stage
The procedure described in example 1 was followed, except that the relative amounts of monomer emulsion 1 and monomer emulsion 2 were adjusted to a weight to weight ratio of 85:15. The z-average particle size was measured at 160nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n Is 12,000g/mol.
EXAMPLE 3 preparation of an aqueous Dispersion of 2-stage blocked Polymer particles with MMA/MAA 10% hard stage
The procedure described in example 1 was followed, except that 1.5 weight percent MMA (3.2 g) was replaced with an equivalent amount (3.2 g) of MAA in the second monomer emulsion. The z-average particle size was 163nm and the percent solids was found to be 52%. M found calculated by gel permeation chromatography n Is 12,000g/mol.
Example 4 preparation of aqueous Dispersion of 2-stage blocked Polymer particles with lower chain transfer agent concentration
The procedure described in example 1 was repeated except that the amount of n-DDM in the first monomer emulsion was reduced from 37g to 18.5g (0.09 mol). Particle size was 168nm and percent solids was found to be 51%. M found calculated by gel permeation chromatography n 20,000g/mol.
Example 5 preparation of aqueous Dispersion of 2-stage blocked Polymer particles with lower chain transfer agent concentration
The procedure described in example 1 was repeated except that the amount of n-DDM in the first monomer emulsion was reduced from 37g to 29g (0.14 mol). The z-average particle size was measured to be 175nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n 15,000g/mol.
Example 6 preparation of aqueous Dispersion of 2-stage blocked Polymer particles with higher chain transfer agent concentration
Repeat in example 1The process is described except that the amount of n-DDM in the first monomer emulsion is increased from 37g to 48g (0.24 mole). The z-average particle size was measured at 192nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n 10,000g/mol.
Example 7-preparation of 2-stage blocked Polymer with MMA and BA in the hard Domain the procedure described in example 1 was followed except that the monomer composition of the second monomer emulsion was BA (10.7 g) and MMA (203.3 g) instead of all MMA. The z-average particle size was found to be 170nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n Is 12,000g/mol.
Comparative example 1 preparation of aqueous Dispersion of 2-stage blocked Polymer particles with lower chain transfer agent concentration
The procedure described in example 1 was repeated except that the amount of n-DDM in the first monomer emulsion was reduced from 37g to 9.6g (0.05 mol). The z-average particle size was 167nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n 34,000g/mol.
Comparative example 2 preparation of aqueous Dispersion of 2-stage blocked Polymer particles with higher chain transfer agent concentration
The procedure described in example 1 was repeated except that the amount of n-DDM in the first monomer emulsion was increased from 37g to 57g (0.28 mol). The z-average particle size was measured to be 164nm and the percent solids was found to be 52%. M found calculated by gel permeation chromatography n 8600g/mol.
Comparative example 3 preparation of an aqueous dispersion of 2-stage blocked Polymer particles with 10% hard Domain of MMA and isobornyl methacrylate
The procedure described in example 1 was repeated except that isobornyl methacrylate (106 g) was substituted for the equivalent amount of MMA (106 g) in the second monomer emulsion. The z-average particle size was measured to be 164nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n Is 12,000g/mol.
Comparative example 4 preparation of an aqueous dispersion of 2-stage blocked Polymer particles with 10% hard domains of styrene
The procedure described in example 1 was repeated except that styrene (214 g) was used in place of MMA in the second monomer emulsion, and the second monomer emulsion was added to the reactor over a feed time of 30 minutes. The z-average particle size was 163nm and the percent solids was found to be 51%. M found calculated by gel permeation chromatography n 13,000g/mol.
Preparation of coating formulations
Coating formulations were prepared from the components listed in table 2 in the order listed. The components were mixed with an overhead stirrer for 10 minutes and then allowed to equilibrate overnight. Emulsion polymers refer to aqueous dispersions of the blocked polymer particles of examples 1-7 and comparative examples 1-5.
TABLE 2 coating formulation
| Component (A) | Quality (g) |
| Emulsion polymers | 39.2 |
| Bayferrox Black 318 pigment | 0.2 |
| Durcal 10CaCO 3 | 57.9 |
| Kollotex 1500 potato starch | 2.5 |
| ACRYSOL TM RM-12W rheology modifier | 1.0 |
| CARBOWAX TM PEG 8000 polyethylene glycol a | 1.0 |
a Only formulations 4-7 and comparative formulations 1 and 2 contained PEG 8000 (see table 2).
Water absorption test
The coating was stretched into 4X 100X 80-mm samples on an aluminum plate. The sample was then left at room temperature for 30 minutes and then baked at 150 ℃ for 30 minutes. The sample was cooled to room temperature and weighed to determine its total mass. The sample was then immersed in 10cm of water for 48h and weighed again. The water uptake is reported as the percent mass difference between the soaked and non-soaked samples.
Foaming
Foaming was evaluated in a ratio of 1-10 as defined below:
10: trace or no surface defects
8: slight bump
6: medium bump
4: heavy bump
2: serious bump
Texture and method for producing the same
Texture was evaluated in a scale of 1-10 as defined below:
10: trace or no surface defects
8: slight pit and pinhole
6: medium pit and pinhole
4: heavy pit and pinhole
2: severe pit and pinhole
Table 3 summarizes the water absorption, foaming and texture results of the coatings prepared from the formulations.
TABLE 3 Water absorption, foaming and coating texture
| Formulation # | Example # | Texture and method for producing the same | Foaming | Water absorption-48 h (%) |
| 1 | Example 1 | 10 | 10 | 5.2 |
| 2 | Example 2 | 9 | 10 | 4.8 |
| 3 | Example 3 | 9 | 10 | 3.7 |
| 4 | Example 4 | 10 | 10 | 7.9 |
| 5 | Example 5 | 10 | 10 | 4.6 |
| 6 | Example 6 | 8 | 10 | 3.4 |
| 7 | Example 1 | 10 | 10 | 3.0 |
| 8 | Example 7 | 10 | 9 | 4.9 |
| Comparative example 1 | Comparative example 1 | 9 | 3 | 11.0 |
| Comparative example 2 | Comparative example 2 | 6 | 6 | 3.4 |
| Comparative example 3 | Comparative example 3 | 3 | 6 | 2.3 |
| Comparative example 4 | Comparative example 4 | 5 | 6 | 2.7 |
Coatings formed from the compositions of examples 1-7 all showed excellent appearance without major drawbacks, as evidenced by a numerical score of at least 8 for texture and blistering. Furthermore, each coating from examples 1-7 had an acceptable water absorption of less than 10%. In contrast, the compositions of the comparative examples all failed in at least one aspect of appearance. The results show the criticality of Mn and high weight fraction of structural units of MMA in the blocked second polymer.
Claims (6)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201962949471P | 2019-12-18 | 2019-12-18 | |
| US62/949471 | 2019-12-18 | ||
| PCT/US2020/061230 WO2021126454A1 (en) | 2019-12-18 | 2020-11-19 | Preparation of an aqueous dispersion of occluded polymer particles |
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| CN114787205A CN114787205A (en) | 2022-07-22 |
| CN114787205B true CN114787205B (en) | 2024-04-16 |
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| US (1) | US12404351B2 (en) |
| EP (1) | EP4077417B1 (en) |
| JP (1) | JP7651572B2 (en) |
| KR (1) | KR20220118472A (en) |
| CN (1) | CN114787205B (en) |
| CA (1) | CA3161860C (en) |
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| CN1667063A (en) * | 2004-03-09 | 2005-09-14 | 罗姆和哈斯公司 | Aqueous dispersion of polymer particles |
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| CN114787205A (en) | 2022-07-22 |
| US20230052817A1 (en) | 2023-02-16 |
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| JP7651572B2 (en) | 2025-03-26 |
| US12404351B2 (en) | 2025-09-02 |
| WO2021126454A1 (en) | 2021-06-24 |
| MX2022007243A (en) | 2022-07-13 |
| EP4077417B1 (en) | 2023-12-27 |
| KR20220118472A (en) | 2022-08-25 |
| EP4077417A1 (en) | 2022-10-26 |
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